Role of N-Oxide Moieties in Tuning Supramolecular Gel-State Properties.

ABSTRACT

The role of specific interactions in the self-assembly process of low molecular weight gelators (LMWGs) was studied by altering the nonbonding interactions responsible for gel formation via structural modification of the gelator/nongelator. This was achieved by modifying pyridyl moieties of bis(pyridyl) urea-based hydrogelator (4-BPU) and the isomer (3-BPU) to pyridyl N-oxide compounds (L1 and L2, respectively). The modification of the functional groups resulted in the tuning of the gelation properties of the parent gelator, which induced/enhanced the gelation properties. The modified compounds displayed better mechanical and thermal stabilities and the introduction of the N-oxide moieties had a prominent effect on the morphologies of the gel network, which was evident from the scanning electron microscopy (SEM) images. The effect of various interactions due to the introduction of N-oxide moieties in the gel network formation was analyzed by comparing the solid-state interactions of the compounds using single crystal X-ray diffraction and computational studies, which were correlated with the enhanced gelation properties. This study shows the importance of specific nonbonding interactions and the spatial arrangement of the functional groups in the supramolecular gel network formation.